KR20210013119A - Photosensitive resin composition and method of forming resist pattern - Google Patents

Abstract

A photosensitive resin composition for obtaining a cured resin product by developing after heating after exposure is provided. The photosensitive resin composition is a compound having (A) 10% by mass to 90% by mass of an alkali-soluble polymer and (B) 5% by mass to 70% by mass of ethylenically unsaturated double bond based on the total solid content mass. And (C) 0.01% by mass to 20% by mass of a photoinitiator. The alkali-soluble polymer (A) has an inorganic value (I value) of 720 or less; The alkali-soluble polymer (A) has a solubility parameter (sp value) of 21.45 MPa ^1/2 or less; Alternatively, the photosensitive resin composition contains an alkali-soluble polymer (A-1) containing 52% by mass or more of structural units derived from styrene and/or a styrene derivative as a monomer component, based on the total solid content mass in the photosensitive resin composition. Thus, it contains 3% by mass or more.

Description

Photosensitive resin composition and method of forming resist pattern

The present invention relates to a photosensitive resin composition and a method of forming a resist pattern.

In electronic devices such as PCs and mobile phones, printed wiring boards or the like are used to mount components, semiconductors, and the like. As a resist for manufacturing a printed wiring board, etc., conventionally, a photosensitive resin laminate having a support layer, a photosensitive resin layer laminated on the support layer, and a protective layer laminated on the photosensitive resin layer as necessary, so-called dry film photoresist (Hereinafter, it may be referred to as "DF".) is used. As the photosensitive resin layer, at present, an alkali developing type using a weak alkaline aqueous solution as a developer is generally used.

As a method of manufacturing a printed wiring board or the like using DF, the following methods are mentioned, for example. When DF has a protective layer, the protective layer is first peeled off. After that, DF is laminated on a substrate such as a substrate for permanent circuit production such as a copper clad laminate or a flexible substrate, using a laminator or the like. The laminated DF is exposed through a wiring pattern mask film or the like. If necessary, the support layer is peeled off, and the photosensitive resin layer of the uncured portion (e.g., equivalent to the unexposed portion in the negative type) is dissolved or dispersed and removed with a developer, and a cured resist pattern (hereinafter, simply `` It may be called "resist pattern".) is formed.

After the formation of the resist pattern, there are two methods of forming a circuit. The first method is an etching method including removing the substrate surface not covered by the resist pattern (e.g., the copper surface of the copper clad laminate) by etching and removing the resist pattern portion with an alkaline aqueous solution stronger than the developer. . In the second method, plating treatment of copper, solder, nickel, tin, etc. is performed on the substrate surface, the resist pattern portion is removed in the same manner as in the first method, and then the surface of the substrate (for example, copper coating It is a plating method including etching the copper surface of a laminated plate). As a solution in etching, a solution of cupric chloride, ferric chloride, or a copper ammonia complex solution is used.

In recent years, along with the miniaturization and weight reduction of electronic devices, miniaturization and high density of printed wiring boards are in progress, and high-performance DFs that provide high resolution and high adhesion are required in the manufacturing process as described above. For example, in Patent Document 1, a photosensitive resin composition in which resolution is improved by a specific thermoplastic resin, a monomer, and a photopolymerizable initiator is described. Patent Document 2 describes a method for forming a resist pattern, including a step of heating the exposed photosensitive resin composition layer and the substrate together under pressure using a pressure heating mechanism. Patent Document 3 describes a method of forming a resist pattern, including a step of exposing, heat treating, and developing a laminate in which (a) a photosensitive layer and (b) a resin layer are formed on a substrate. Patent Document 4 describes a method for forming a resist pattern, including a step of leaving the laminate in a reduced pressure atmosphere or a low oxygen concentration atmosphere at least between exposure and heat treatment. In Patent Literature 5, various additives which are optionally included in the photosensitive resin layer of DF are described. In Patent Document 6, a protective layer preferably applied to DF is described.

Japanese Patent Laid-Open Publication No. 2010-249884 Japanese Unexamined Patent Publication No. 2014-191318 Japanese Laid-Open Patent Publication No. 2016-224161 Japanese Unexamined Patent Publication No. 2016-224162 Japanese Unexamined Patent Publication No. 2013-156369 Japanese Laid-Open Patent Publication No. 59-202457

After the exposure step, in some cases, a heating step (heating after exposure: PEB) is performed on the photosensitive resin layer, and then development may be performed. By performing this heating process, further improvement of high resolution and high adhesion becomes possible. However, even if the heating process was performed after exposure, the improvement of adhesion was insufficient in the conventional photosensitive resin composition. Moreover, when a long time after exposure passes, even if a heating process after exposure is performed, good adhesiveness may not be obtained.

The present invention has been proposed in view of such a conventional situation, and an object of the present invention is to provide a photosensitive resin composition capable of remarkably improving adhesion when developed after heating after exposure. In particular, in a preferred embodiment, an object thereof is to provide a photosensitive resin composition that exhibits good adhesion even when a long time has elapsed from exposure to heating.

The inventors of the present application have repeatedly studied intensively in order to solve the above problems, and as a result, alkali-soluble polymer having an inorganic value (I value) in a specific range; Alkali-soluble polymer having a solubility parameter (sp value) in a specific range; Or, it found out that the said subject can be solved by the photosensitive resin composition containing the alkali-soluble polymer (A-1) which has a structural unit of a specific structure, and came to complete this invention. Examples of the embodiments of the present invention are shown in Examples [1] to [29] of the following embodiments.

[One]

As a photosensitive resin composition for obtaining a cured resin product after exposure, heating and then developing, wherein the photosensitive resin composition includes the following components based on the total solid content mass of the photosensitive resin composition:

(A) 10% by mass to 90% by mass of alkali-soluble polymer,

(B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond,

(C) 0.01% by mass to 20% by mass of photopolymerization initiator

Including,

The photosensitive resin composition, wherein the inorganic value (I value) of the alkali-soluble polymer (A) is 720 or less.

[2]

The photosensitive resin composition according to item 1, wherein the I value of the alkali-soluble polymer (A) is 635 or less.

[3]

The photosensitive resin composition according to item 2, wherein the alkali-soluble polymer (A) has an I value of 600 or less.

[4]

The photosensitive resin composition according to any one of items 1 to 3, wherein the alkali-soluble polymer (A) has an I value of 300 or more.

[5]

The photosensitive resin composition according to item 4, wherein the alkali-soluble polymer (A) has an I value of 400 or more.

[6]

The photosensitive resin composition according to item 5, wherein the alkali-soluble polymer (A) has an I value of 450 or more.

[7]

The photosensitive resin composition according to item 6, wherein the alkali-soluble polymer (A) has an I value of 500 or more.

[8]

The photosensitive resin composition according to item 7 wherein the alkali-soluble polymer (A) has an I value of 550 or more.

[9]

As a photosensitive resin composition for obtaining a cured resin product after exposure, heating and then developing, wherein the photosensitive resin composition includes the following components based on the total solid content mass of the photosensitive resin composition:

(A) 10% by mass to 90% by mass of alkali-soluble polymer,

(B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond,

(C) 0.01% by mass to 20% by mass of photopolymerization initiator

Including,

The photosensitive resin composition, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.45 MPa ^1/2 or less.

[10]

The photosensitive resin composition according to item 9, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.40 MPa ^1/2 or less.

[11]

The photosensitive resin composition according to item 10, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.20 MPa ^1/2 or less.

[12]

The photosensitive resin composition according to any one of items 9 to 11, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 19.00 MPa ^1/2 or more.

[13]

The photosensitive resin composition according to item 12, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 19.50 MPa ^1/2 or more.

[14]

The photosensitive resin composition according to item 13, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 20.00 MPa ^1/2 or more.

[15]

The photosensitive resin composition according to item 14, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 20.50 MPa ^1/2 or more.

[16]

As a photosensitive resin composition for obtaining a cured resin product after exposure, heating and then developing, wherein the photosensitive resin composition includes the following components based on the total solid content mass of the photosensitive resin composition:

(A) 10% by mass to 90% by mass of alkali-soluble polymer,

(B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond,

(C) 0.01% by mass to 20% by mass of photopolymerization initiator

Including,

The photosensitive resin composition includes, as the alkali-soluble polymer (A), an alkali-soluble polymer (A-1) containing 52% by mass or more of structural units derived from styrene and/or a styrene derivative as a monomer component, and the photosensitive resin composition The photosensitive resin composition containing 3 mass% or more based on the total solid content mass in in.

[17]

The photosensitive resin composition according to item 16, wherein the photosensitive resin composition contains 10% by mass or more of the alkali-soluble polymer (A-1) with respect to the total solid content mass in the photosensitive resin composition.

[18]

The photosensitive resin composition according to item 16 or 17, wherein the alkali-soluble polymer (A-1) contains 55% by mass or more of structural units derived from styrene and/or a styrene derivative as a monomer component.

[19]

The photosensitive resin composition according to item 18, wherein the alkali-soluble polymer (A-1) contains 58 mass% or more of structural units derived from styrene and/or a styrene derivative as a monomer component.

[20]

The photosensitive resin composition according to any one of items 16 to 19, wherein the alkali-soluble polymer (A-1) contains 27% by mass or more of a structural unit derived from (meth)acrylic acid as a monomer component.

[21]

The photosensitive resin composition according to any one of items 16 to 19, wherein the alkali-soluble polymer (A-1) further contains a structural unit derived from benzyl (meth)acrylate as a monomer component.

[22]

The following process:

Step of exposing the layer of the photosensitive resin composition according to any one of items 1 to 21;

A heating step of heating the exposed layer of the photosensitive resin composition; And

Development process of developing the heated layer of the photosensitive resin composition

A method of forming a resist pattern comprising a.

[23]

The method for forming a resist pattern according to item 22, wherein the heating temperature in the heating step is in the range of 30°C to 150°C.

[24]

The method for forming a resist pattern according to item 22 or 23, wherein the heating step is performed within 15 minutes from stopping the exposure.

[25]

The method for forming a resist pattern according to any one of items 22 to 24, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens. .

[26]

The method for forming a resist pattern according to item 25, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern.

[27]

The method for forming a resist pattern according to item 26, wherein the exposure step is performed by a method of exposing with a first laser light having a center wavelength of less than 390 nm and a second laser light having a center wavelength of 390 nm or more.

[28]

The method for forming a resist pattern according to item 27, wherein the center wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less.

[29]

Manufacturing of a circuit board comprising forming a circuit board by preparing a resist pattern on a substrate by the method according to any one of items 22 to 28, and etching or plating the substrate having the resist pattern. Way.

According to the present invention, it is possible to remarkably improve the adhesiveness of a resist pattern when it is developed after heating (PEB) after exposure. In a preferred embodiment, even when a long time elapses from exposure to heating, a photosensitive resin composition that exhibits good adhesion can be provided. In addition, the description described above should not be regarded as disclosing all the embodiments of the present invention and all advantages related to the present invention. Additional embodiments of the present invention and advantages thereof will become apparent by referring to the following description.

Hereinafter, although it demonstrates in detail for the purpose of illustrating an embodiment of the present invention, the present invention is not limited to the present embodiment. In the specification of the present application, the upper and lower limits of each numerical range can be arbitrarily combined.

[Photosensitive resin composition]

The photosensitive resin composition of this embodiment is a photosensitive resin composition for obtaining a cured resin product by developing after exposure and heating. The photosensitive resin composition is based on the total solid content mass of the photosensitive resin composition, (A) 10% by mass to 90% by mass of alkali-soluble polymer and (B) 5% by mass to 70% by mass of ethylenically unsaturated double bond The compound which has and (C) 0.01 mass%-20 mass% of photoinitiators are contained.

<(A) Alkali-soluble polymer>

In the present embodiment, the photosensitive resin composition may have an inorganic value (I value) of 720 or less of the alkali-soluble polymer (A). Here, "I value" is also called "Inorganic Value", and represents the degree of physical properties mainly due to electrical affinity. "O value" is also called "organic value", and represents the degree of physical properties mainly due to Van der Waals force. The I/O value is a parameter indicating a measure of lipophilicity/hydrophilicity of a compound or substituent, and is determined based on the I value and O value inherent to the compound or substituent. The larger the I/O value, the higher the inorganicity. For more information on I/O values, refer to Yoshio Koda's, "Organic Conceptual Map", Sankyo Publishing, 1984, etc.

In this embodiment, in the photosensitive resin composition, the solubility parameter (sp value) of the alkali-soluble polymer (A) may be 21.45 MPa ^1/2 or less. The solubility parameter (sp value) is the square root of the cohesive energy density of a substance, and for details and calculation methods, Toshinao Okitsu, ``The role of the solubility parameter (SP) in the solubility theory (first report)'' , Japanese Journal of Adhesion, 1993, vol.29, No.5, pp.8-15. In the specification of the present application, the sp value means a value calculated by the Okitsu method.

In this embodiment, the photosensitive resin composition, as an alkali-soluble polymer (A), contains an alkali-soluble polymer (A-1) containing 52% by mass or more of structural units derived from styrene and/or a styrene derivative as a monomer component, You may contain 3 mass% or more with respect to the total solid content mass in a photosensitive resin composition.

The photosensitive resin composition of the present embodiment has any one or more of the inorganic value (I value), the solubility parameter (sp value), or the alkali-soluble polymer (A-1), and is developed after heating after exposure. When it does, the adhesion can be remarkably improved. In the photosensitive resin composition of this embodiment, the inorganic value (I value) of an alkali-soluble polymer (A) may be 720 or less, and a solubility parameter (sp value) may be 21.45 MPa ^1/2 or less; The inorganic value (I value) of the alkali-soluble polymer (A) is 720 or less, and the alkali-soluble polymer (A-1) may be included in an amount of 3% by mass or more with respect to the total solid content mass; The solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.45 MPa ^1/2 or less, and the alkali-soluble polymer (A-1) may be included in an amount of 3% by mass or more with respect to the total solid content mass; Alternatively, the inorganic value (I value) of the alkali-soluble polymer (A) is 720 or less, the solubility parameter (sp value) is 21.45 MPa ^1/2 or less, and the alkali-soluble polymer (A-1) is added to the total solid content mass. You may contain 3 mass% or more with respect to it.

In general, if the dry film resist obtained from the photosensitive resin composition is not heated immediately after exposure, there is a tendency that the adhesion is not well improved. On the other hand, the dry film resist obtained from the photosensitive resin composition of the present embodiment can exhibit good adhesion even if a long time elapses from exposure to heating, and a fine resist pattern can be obtained.

The reason for improving the adhesion when developing after heating after exposure is not limited to the theory, but the inventors estimate as follows. When the inorganic value (I value) of the alkali-soluble polymer is 720 or less, the electrical affinity of the alkali-soluble polymer is low, the permeability during development is suppressed, and the swelling and dissolution resistance is increased. As a result, it is considered that even a fine resist pattern is maintained without being damaged by development. In addition, when the elapsed time from exposure to heating increases, radicals generated during exposure collide with oxygen in the alkali-soluble polymer and become deactivated, so that the effect of PEB is reduced. However, the alkali-soluble polymer having a low electrical affinity is considered to maintain the effect of PEB even if the elapsed time is prolonged, because water does not ionize well, does not contain water molecules well, and the movement of oxygen is hindered. If the solubility parameter (sp value) of the alkali-soluble polymer is 21.45 MPa ^1/2 or less, the hydrophobicity of the alkali-soluble polymer is high, and the swelling and dissolution resistance during development is high, and as a result, even a fine resist pattern is damaged by development. It seems to be kept without work. In addition, since the alkali-soluble polymer having high hydrophobicity has low hygroscopicity and impedes the movement of oxygen through a water molecule, it is considered that the effect of PEB is maintained even if the elapsed time from exposure to heating is prolonged. The photosensitive resin composition contains 3% by mass or more of the alkali-soluble polymer (A-1) with respect to the total mass of the solid content in the photosensitive resin composition, so that the mobility of the resin is significantly improved by heating after exposure, and the hydrophobicity of the styrene skeleton and the carbon- The reactivity of the carbon double bond can be highly compatible. As a result, adhesion can be remarkably improved. And since the adhesion is remarkably improved, even if a long time elapses after exposure, good adhesion can be obtained.

The upper limit of the inorganic value (I value) of the alkali-soluble polymer is preferably 635 or less, or 600 or less, and the lower limit is preferably 300 or more, 350 or more, 400 or more, 450 or more, 500 or more, or 550 or more. . When the inorganic value (I value) is 350 or more, there is an advantage that the residue of the alkali-soluble polymer is hardly left between fine wirings. Alkali-soluble polymers may be used alone or in combination of two or more. When two or more types are mixed and used, the inorganic value (I value) as an alkali-soluble polymer mixture is preferably within a specific range in the present embodiment. The inorganic value (I value) of the mixture can be obtained as the sum of the values obtained by multiplying the I value of each component by the weight fraction, assuming that there is causticity.

The upper limit of the solubility parameter (sp value) of the alkali-soluble polymer is preferably 21.40 MPa ^1/2 or less, or 21.20 MPa ^1/2 or less, and the lower limit is preferably 19.00 MPa ^1/2 or more and 19.50 MPa ^{1/ It is 2} or more, 20.00 MPa ^1/2 or more, or 20.50 MPa ^1/2 or more. When the solubility parameter (sp value) is 19.00 MPa ^1/2 or more, there is an advantage in that the residue of the alkali-soluble polymer is hardly left between fine wirings. Alkali-soluble polymers may be used alone or in combination of two or more. When two or more types are mixed and used, the solubility parameter (sp value) as an alkali-soluble polymer mixture is preferably within a specific range in the present embodiment. The solubility parameter (sp value) as a mixture is assumed to be caustic, and can be calculated as the sum of the sp value of each component multiplied by the weight fraction.

In this embodiment, the alkali-soluble polymer refers to a polymer that is easily soluble in an alkaline substance so that the resulting photosensitive resin layer has developability and releasability with respect to an aqueous alkali solution. More specifically, the amount of the carboxyl group contained in the alkali-soluble polymer is preferably 100 g to 600 g, or 250 g to 450 g in terms of acid equivalent. The acid equivalent is the mass (unit: gram) of a polymer having 1 equivalent of carboxyl group in the molecule. The carboxyl group in the alkali-soluble polymer imparts developability and releasability to the aqueous alkali solution to the photosensitive resin layer. When the acid equivalent is 100 or more, development resistance, resolution, and adhesion are improved. It is more preferable that the acid equivalent is 250 g or more. When the acid equivalent is 600 g or less, developability and peelability are improved. It is more preferable that the acid equivalent is 450 g or less. In the specification of the present application, an acid equivalent is a value measured by a potentiometric titration method titrated with a 0.1 mol/L aqueous NaOH solution using a potentiometric titration device.

It is preferable that the weight average molecular weight (Mw) of an alkali-soluble polymer is 5,000-500,000. When the weight average molecular weight is 500,000 or less, resolution and developability are improved. The weight average molecular weight is more preferably 100,000 or less, 70,000 or less, 60,000 or less, or 50,000 or less. When the weight average molecular weight is 5,000 or more, it is easier to control the properties of the developed aggregate and the properties of the unexposed film such as edge fuse properties and cut chip properties in the photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, or 20,000 or more. The edge fuse property refers to the degree of easiness of protruding the photosensitive resin layer from the end face of the roll when the photosensitive resin laminate is wound up in a roll shape. The cut chip property refers to the degree of ease of scattering of chips when the unexposed film is cut with a cutter. When this chip adheres to the upper surface of the photosensitive resin laminate or the like, it is transferred to the mask in a subsequent exposure process or the like, resulting in defective products.

The dispersion degree defined as the ratio (Mw/Mn) of the weight average molecular weight (Mw) of the alkali-soluble polymer and the number average molecular weight (Mn) is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and 1.0 to It is more preferable that it is 4.0, and it is still more preferable that it is 1.0-3.0. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble polymer are both values in terms of polystyrene measured by gel permeation chromatography (GPC).

In order to provide higher adhesion when developed after heating after exposure, in particular, better adhesion when a long time elapses after exposure, the alkali-soluble polymer contains constituent units derived from a monomer component having an aromatic hydrocarbon group. It is desirable. As an aromatic hydrocarbon group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, etc. are mentioned, for example. The lower limit of the amount of the monomer component having an aromatic hydrocarbon group in the alkali-soluble polymer is preferably 20% by mass or more, 40% by mass or more, and 50% by mass based on the total mass of all monomer components of the alkali-soluble polymer. It is not less than 55 mass%, or not less than 60 mass%. The upper limit of the amount of the monomer component having an aromatic hydrocarbon group is not limited, but may be, for example, 95% by mass or less, or 80% by mass or less. When the photosensitive resin composition contains plural kinds of alkali-soluble polymers, the amount of the monomer component having an aromatic hydrocarbon group is determined as a weight average value.

As a monomer having an aromatic hydrocarbon group, a monomer having an aralkyl group, styrene, and a styrene derivative may be mentioned, for example. When the alkali-soluble polymer contains a structural unit derived from a monomer having an aralkyl group, styrene, or a styrene derivative, higher resolution can be provided. As such an alkali-soluble polymer, a copolymer including methacrylic acid, benzyl methacrylate, and styrene, and a copolymer including methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene are preferable, for example.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (except for a benzyl group), and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable. Examples of the comonomer having a phenylalkyl group include phenylethyl (meth)acrylate. Examples of the comonomer having a benzyl group include (meth)acrylate having a benzyl group, such as benzyl (meth)acrylate, and chlorobenzyl (meth)acrylate; And vinyl monomers having a benzyl group, for example, vinyl benzyl chloride, and vinyl benzyl alcohol. As a comonomer having a benzyl group, preferably, it is benzyl (meth)acrylate.

The alkali-soluble polymer is preferably a polymer of a first monomer having a polymerizable unsaturated group and a carboxyl group in the molecule, and more preferably a copolymer of the first monomer and a non-acidic second monomer having a polymerizable unsaturated group in the molecule. When the alkali-soluble polymer contains a monomer component having an aromatic hydrocarbon group, the alkali-soluble polymer is preferably a copolymer of a monomer having an aromatic hydrocarbon group and at least one type of the first monomer and/or at least one type of the second monomer. .

The first monomer is a monomer having a polymerizable unsaturated group and a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half-ester. The first monomer is preferably (meth)acrylic acid. In the specification of the present application, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acryloyl group" means an acryloyl group or methacryloyl group, and "(meth)acrylate" "Acrylate" or "methacrylate" is meant.

The amount of the first monomer in the alkali-soluble polymer is preferably 10% by mass to 50% by mass, based on the total mass of all monomer components constituting the alkali-soluble polymer. When the amount of the first monomer is 10% by mass or more, better developability can be provided and edge fuse properties can be more easily controlled. The amount of the first monomer is more preferably 15% by mass or more, or 20% by mass or more. When the amount of the first monomer is 50% by mass or less, higher resolution of the resist pattern, better skirt shape, and higher chemical resistance can be provided. The amount of the first monomer is more preferably 35% by mass or less, 32% by mass or less, or 30% by mass or less.

The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule. As the second monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2- (Meth)acrylate compounds such as ethylhexyl (meth)acrylate; Vinyl alcohol ester compounds such as vinyl acetate; And (meth)acrylonitrile, etc. are mentioned. The second monomer is preferably at least one selected from the group consisting of methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate.

It is preferable that the amount of the second monomer in the alkali-soluble polymer is 10% by mass to 50% by mass, based on the total mass of all monomer components constituting the alkali-soluble polymer. When the amount of the second monomer is 10% by mass or more, better developability can be provided and edge fuse properties can be more easily controlled. The amount of the second monomer is more preferably 15% by mass or more, or 20% by mass or more. When the amount of the second monomer is 50% by mass or less, higher resolution of the resist pattern, better skirt shape, and higher chemical resistance can be provided. The amount of the second monomer is more preferably 35% by mass or less, 32% by mass or less, or 30% by mass or less.

The alkali-soluble polymer may be composed of only one alkali-soluble polymer, or may be a mixture of two or more alkali-soluble polymers. In the case of a mixture of two or more alkali-soluble polymers, the alkali-soluble polymer includes two or more alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group, or an alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group. It is preferable to contain at least one type and at least one type of alkali-soluble polymer that does not contain a monomer component having an aromatic hydrocarbon group. In the latter case, the amount of the alkali-soluble polymer containing the monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, 70% by mass or more, 80% by mass or more, and 90% by mass relative to the total mass of the alkali-soluble polymer. Or more or 95% by mass or more.

It is more preferable that the alkali-soluble polymer is an alkali-soluble polymer (A-1) containing a structural unit of styrene and/or a styrene derivative as a monomer component. Examples of the styrene derivative include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer.

The amount of the alkali-soluble polymer (A-1) contained in the photosensitive resin composition is based on the total solid content mass in the photosensitive resin composition, preferably, 3% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass It is at least 20 mass%, at least 25 mass%, or at least 30 mass%.

The total amount of styrene and/or styrene derivative, which is a constituent unit of the alkali-soluble polymer (A-1), is preferably 52% by mass or more and 55% by mass based on the total mass of the alkali-soluble polymer (A-1). It is 58 mass% or more, or 60 mass% or more. By containing 52% by mass or more of structural units derived from styrene and/or styrene derivatives, heating after exposure and then developing, the mobility of the resin is significantly improved by heating even in a system with a large content of the styrene skeleton. The hydrophobicity of the skeleton and the reactivity of the carbon-carbon double bond are highly compatible. As a result, adhesion can be remarkably improved. And by remarkably improving the adhesiveness, good adhesiveness can be obtained even when the elapsed time after exposure becomes long.

When the content of the styrene skeleton is small, it is easier to obtain desired reactivity and adhesion without excessively deteriorating the mobility of the resin (cured resin obtained). Moreover, since radicals in the system are deactivated when a long time elapses after exposure, the effect of improving adhesion by heating after exposure decreases with time. From this point of view, the total amount of styrene and/or styrene derivative, which is a constituent unit of the alkali-soluble polymer (A-1), is preferably 90% by mass or less based on the total mass of the alkali-soluble polymer (A-1). , 80 mass% or less, 75 mass% or less, or 70 mass% or less.

The alkali-soluble polymer (A-1) is derived from (meth)acrylic acid as a monomer component in order to provide higher adhesion when developed after heating after exposure, especially better adhesion when a long time elapses after exposure. It is preferable to further include a structural unit to be described. The amount of the structural unit derived from (meth)acrylic acid is, based on the total mass of the alkali-soluble polymer (A-1), preferably 25% by mass or more, 26% by mass or more, 27% by mass or more, 28% by mass Or more, or 29 mass% or more. From the same viewpoint, the amount of the structural unit derived from (meth)acrylic acid is, based on the total mass of the alkali-soluble polymer (A-1), preferably 35 mass% or less, 32 mass% or less, or 30 mass% Below.

In order to provide higher adhesion when developed after heating after exposure, in particular, better adhesion after a long time after exposure, the alkali-soluble polymer (A-1) is used as a monomer component, benzyl (meth)acrylate. It is preferable to further include a structural unit derived from. The amount of the structural unit derived from benzyl (meth)acrylate is based on the total mass of the alkali-soluble polymer (A-1), preferably 5% by mass or more, 10% by mass or more, 15% by mass or more, or It is 20 mass% or more. From the same viewpoint, the amount of the constituent unit derived from benzyl (meth)acrylic acid is based on the total mass of the alkali-soluble polymer (A-1), preferably 35% by mass or less, 32% by mass or less, or 30% by mass % Or less.

The weight average value Tg ^total of the glass transition temperature Tg of the alkali-soluble polymer (A) is preferably 30°C or more and 150°C or less. When the Tg ^total of the alkali-soluble polymer is 150° C. or less, it is possible to provide higher adhesion when developed after heating after exposure, particularly, better adhesion when a long time elapses after exposure. The Tg ^total of the alkali-soluble polymer is more preferably 135°C or less, 130°C or less, 125°C or less, 120°C or less, or 110°C or less. When the Tg ^total of the alkali-soluble polymer is 30° C. or higher, it is possible to provide higher resistance to fuse. The Tg ^total of the alkali-soluble polymer is more preferably 40°C or higher, 50°C or higher, or 60°C or higher.

The amount of the alkali-soluble polymer (A) contained in the photosensitive resin composition is, based on the total solid content mass of the photosensitive resin composition, preferably 10 mass% to 90 mass%, 30 mass% to 70 mass%, or 40 mass It is%-60 mass %. When the amount of the alkali-soluble polymer in the photosensitive resin composition is 90% by mass or less, it is easier to control the development time. When the amount of the alkali-soluble polymer in the photosensitive resin composition is 10% by mass or more, higher anti-fuse resistance can be provided.

Synthesis of the alkali-soluble polymer (A) can be carried out by diluting a single or plural kinds of monomers constituting the alkali-soluble polymer with a solvent, adding an appropriate amount of a radical polymerization initiator, and stirring by heating to perform polymerization. As a solution used for polymerization, solvents, such as acetone, methyl ethyl ketone, and isopropanol, are mentioned. Examples of the radical polymerization initiator include benzoyl peroxide and azoisobutyronitrile. Instead of diluting all of the monomers with a solution at once, synthesis may be performed while dropping a part of the mixture of monomers into the reaction solution. After completion of the reaction, a solvent may be further added and adjusted to a desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization are mentioned.

<(B) Compound having ethylenically unsaturated double bond>

Compound (B) having an ethylenically unsaturated double bond includes a compound having a (meth)acryloyl group in its molecule in order to provide better curability of the resin composition and higher compatibility with an alkali-soluble polymer. desirable. The number of (meth)acryloyl groups may be 1 or more per 1 molecule of compound (B). From the viewpoint of providing better peelability and flexibility of the cured film, examples of the compound having one (meth)acryloyl group include a compound obtained by adding (meth)acrylic acid to one end of the polyalkylene oxide; A compound obtained by adding (meth)acrylic acid to one end of the polyalkylene oxide, and forming an alkyl ether or allyl ether at the other end; And phthalic acid-based compounds.

Examples of the compound having one (meth)acryloyl group include phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group; 4-Normalnonylphenoxyheptaethylene glycol di, which is a (meth)acrylate of a compound obtained by adding an average of 2 moles of propylene oxide to the polypropylene glycol and an average of 7 moles of ethylene oxide to the nonylphenol Propylene glycol (meth)acrylate; 4-Normalnonylphenoxypentaethylene glycol mono, a (meth)acrylate of a compound in which polypropylene glycol to which an average of 1 mol of propylene oxide is added and polyethylene glycol to which an average of 5 mol of ethylene oxide is added to nonylphenol is added Propylene glycol (meth)acrylate; And 4-normal nonylphenoxyoctaethylene glycol (meth)acrylate, which is an acrylate of a compound in which polyethylene glycol to which an average of 8 moles of ethylene oxide is added is added to nonylphenol (for example, manufactured by Toa Synthetic Co., Ltd., M-114), etc. are mentioned. From the viewpoint of providing higher sensitivity, resolution, and adhesion, as a compound having one (meth)acryloyl group, γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-о -Phthalate is also mentioned.

As a compound having two (meth)acryloyl groups, for example, a compound having a (meth)acryloyl group at both ends of an alkylene oxide chain, and an ethylene oxide chain and a propylene oxide chain are randomly or blocked. And compounds having (meth)acryloyl groups at both ends of the alkylene oxide chain.

As a compound having two (meth)acryloyl groups, for example, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, hepta ethylene Glycol di (meth) acrylate, octaethylene glycol di (meth) acrylate, nona ethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and at both ends of the 12 mol ethylene oxide chain ( Polyethylene glycol (meth)acrylates such as compounds having a meth)acryloyl group; And polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, and polyalkylene oxide di(meth)acrylate compounds containing an ethylene oxide group and a propylene oxide group in a molecule|numerator, etc. are mentioned. As a polyalkylene oxide di(meth)acrylate compound containing an ethylene oxide group and a propylene oxide group in the molecule, for example, an average of 3 moles of ethylene at both ends of the polypropylene glycol to which an average of 12 moles of propylene oxide is added Dimethacrylate of glycol to which oxide was further added; Dimethacrylates of glycols each obtained by adding an average of 15 moles of ethylene oxide to both ends of the polypropylene glycol to which an average of 18 moles of propylene oxide has been added are mentioned. More specifically, FA-023M, FA-024M, FA-027M (product name, Hitachi Chemical Industries make), etc. are mentioned. These are preferable because they can provide higher flexibility, resolution, and adhesion.

As an example of a compound having two (meth)acryloyl groups in the molecule, from the viewpoint of providing higher resolution and adhesion, a compound having (meth)acryloyl groups at both ends is obtained by modifying bisphenol A with alkylene oxide. Can be lifted. Specifically, the following general formula (I):

[Formula 1]

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ and n ₃ are each independently 1 to 39 Is an integer of, and n ₁ + n ₃ is an integer of 2 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29, and n ₂ + n ₄ is an integer of 0 to 30 The arrangement of the repeating units of, -(AO)- and -(BO)- may be random or block. And, in the case of a block, any of -(AO)- and -(BO)- may be on the side of the bisphenyl group. The compound represented by} is preferable.

From the viewpoint of providing higher resolution and adhesion, dimethacrylate of polyethylene glycol in which an average of 5 moles of ethylene oxide is added to both ends of bisphenol A, and an average of 2 moles of ethylene oxide are added to both ends of bisphenol A. Dimethacrylate of polyethylene glycol and dimethacrylate of polyethylene glycol in which an average of 1 mol of ethylene oxide is added to both ends of bisphenol A are preferable. The aromatic ring in the general formula (I) may have a hetero atom and/or a substituent.

As a hetero atom, a halogen atom etc. are mentioned, for example. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, and a dialkyl group having 2 to 20 carbon atoms. Alkylamino group, nitro group, cyano group, carbonyl group, mercapto group, alkyl mercapto group having 1 to 10 carbon atoms, aryl group, hydroxyl group, hydroxyalkyl group having 1 to 20 carbon atoms, carboxyl group, carboxy having 1 to 10 carbon atoms in the alkyl group Alkyl group, an acyl group having 1 to 10 carbon atoms of an alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, N-alkylcarbamoyl group or a group containing a heterocycle, and an aryl group substituted with a substituent thereof. These substituents may form a condensed ring. The hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom. When the aromatic ring in General Formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

As a compound having 3 or more (meth)acryloyl groups in the molecule, it has 3 moles or more of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and ethyleneoxy group, propyleneoxy group, butyleneoxy group, etc. A compound obtained by making an alcohol obtained by adding an alkyleneoxy group of (meth)acrylate is mentioned. In this case, examples of the compound that can serve as the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanurate ring, and the like. As a compound having 3 or more (meth)acryloyl groups, tri(meth)acrylates, for example, ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, penta Erythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.; Tetra(meth)acrylate, such as ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.; Penta(meth)acrylate, for example, dipentaerythritol penta(meth)acrylate, etc.; And hexa(meth)acrylate, for example, dipentaerythritol hexa(meth)acrylate, etc. are mentioned. The compound having 3 or more (meth)acryloyl groups is preferable from the viewpoint of resolution, adhesion, and resist skirt shape, and more preferably, it has 3 or more methacrylic groups.

As trimethylolpropane tri(meth)acrylate, from the viewpoint of high flexibility and adhesion, and suppressing bleed out, for example, trimethacrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane, and trimethyl Trimethacrylate obtained by adding an average of 30 moles of ethylene oxide to allpropane is preferred.

As tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferable. Pentaerythritol tetra(meth)acrylate may be, for example, tetra(meth)acrylate in which a total of 1 to 40 moles of alkylene oxide is added to the four terminals of pentaerythritol. As hexa(meth)acrylate, for example, at the six ends of dipentaerythritol, hexa(meth)acrylate and dipentaerythritol in which 1 to 40 moles of ethylene oxide are added in total Hexa(meth)acrylate to which a total of 1 to 20 moles of ε-caprolactone is added is preferred.

The (meth)acrylate compounds may be used independently or in combination, respectively. The photosensitive resin composition is a compound (B) having an ethylenically unsaturated bond, and may also contain other compounds. Other compounds include a (meth)acrylate having a urethane bond, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, and a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid. The obtained compound, and 1,6-hexanediol di(meth)acrylate, etc. are mentioned.

The amount of the compound (B) having an ethylenically unsaturated double bond contained in the photosensitive resin composition is preferably 5% by mass to 70% by mass, based on the total solid content mass in the photosensitive resin composition. When the amount of the compound (B) is 5% by mass or more, it is preferable from the viewpoint of sensitivity, resolution, and adhesion. The amount of the compound (B) is more preferably 20% by mass or more, or 30% by mass or more. When the amount of the compound (B) is 70% by mass or less, it is preferable from the viewpoint of suppressing the delay in peeling of the edge fuse and the cured resist. The amount of the compound (B) is more preferably 50% by mass or less.

In this embodiment, compound (B) is a compound having an ethylenically unsaturated double bond, and the following general formula (II):

[Formula 2]

In formula (II), A may be a compound (B1) having a structure represented by a C4 or more divalent hydrocarbon group. When compound (B) contains compound (B1), it may consist only of compound (B1), or, together with compound (B1), have an ethylenically unsaturated double bond, and a structure represented by the general formula (II) You may further contain the compound (B2) which does not have.

[Compound (B1)]

The number of ethylenically unsaturated double bonds contained in the compound (B1) may be 1 or more, preferably 2 or more, more preferably 2 from the viewpoint of improving the film remaining properties during development and the physical properties of the cured product. It is 6 or more, more preferably 2 or more and 4 or less, and even more preferably 2 or more. The ethylenically unsaturated double bond contained in the compound (B1) is a group selected from an acryloyl group and a methacryloyl group from the viewpoint of compatibility with an alkali-soluble polymer and curability of the photosensitive resin composition (hereinafter, ``(meth ) It is also called "acryloyl group".) is preferable.

As compound (B1), for example, the following general formula (III):

[Formula 3]

(In the formula, (AO) moiety corresponds to the above (II), A is a C4 or more divalent hydrocarbon group, preferably a C4 to C8 divalent hydrocarbon group, and B ¹ and B ² are each independently Is an ethylene group or a propylene group, the arrangement of (B ¹ -O), (AO), and (B ² -O) may be random or block, n1 is an integer from 0 to 50, and n2 is from 2 to It is an integer of 100, n3 is an integer of 0-50, R<^1> and R<^2> are each independently a hydrogen atom or a methyl group. The compound represented by} is mentioned.

A in formula (III) is a C4 or more divalent hydrocarbon group, preferably a C4-8 divalent hydrocarbon group. This divalent hydrocarbon group may be linear, branched, or contain an alicyclic. A is preferably a linear or branched alkylene group. As a specific example of A, for example, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, butane-2,3-diyl group, butane-1,2-diyl group, pentane-2,3-di Diary, a pentane-1,4-diyl group, a 2,2-dimethyl-1,3-propylene group, a hexane-1,5-diyl group, etc. are mentioned. As A, it is preferably a C4 divalent hydrocarbon group, more preferably a C4 alkylene group, and particularly preferably a tetramethylene group. n2 is an integer of 2 to 100, preferably an integer of 3 to 75, and more preferably an integer of 4 to 50.

B ¹ and B ² in formula (III) may each independently be selected from 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, or the like. n1 and n3 are each independently an integer of 0 to 50, preferably an integer of 0 to 30, an integer of 0 to 20, or an integer of 0 to 10. It is preferable that n1+n3 is an integer of 0-10. The arrangement of (B ¹ -O), (AO), and (B ² -O) may be random or block. R ¹ and R ² are each independently a hydrogen atom or a methyl group.

As the compound (B1), a compound in which both n1 and n3 in formula (III) are 0, and both n1 and n3 in formula (III) are 1 to 50 (preferably 1 to 30, 1 to It is preferably selected from 20, or 1 to 10) phosphorus compounds. Examples of the compound in which both n1 and n2 in formula (III) are 0 include di(meth)acrylate of polytetramethylene glycol to which 2 to 100 moles of tetramethylene oxide has been added. In formula (III), as a compound in which both n1 and n2 are 1 to 50, for example, ethylene oxide or propylene oxide is added to both ends of polytetramethylene glycol to which 2 to 100 mol of tetramethylene oxide is added. The di(meth)acrylate of polyalkylene glycol added by 1 to 50 mol, respectively, etc. are mentioned.

Compound (B1) may consist of only one type of compound, or two or more different types of at least ^one of 1, B ¹ , B ² , R ¹ , R ² , n1, n2, and n3 in formula (III) It may be a mixture of compounds.

Compound (B2) is a compound which has an ethylenically unsaturated double bond and does not have a structure represented by formula (II). The number of ethylenically unsaturated double bonds contained in the compound (B2) may be 1 or more, preferably 2 or more, more preferably 2 from the viewpoint of improving the film remaining properties during development and the physical properties of the cured product. It is not less than 10 　, not more than 2, not more than 8, or not less than 2 and not more than 6. The ethylenically unsaturated double bond contained in the compound (B2) is preferably a (meth)acryloyl group from the viewpoint of compatibility with an alkali-soluble polymer and curability of the photosensitive resin composition.

In the compound (B2), as a compound having two (meth)acryloyl groups, for example, a compound having a (meth)acryloyl group at both ends of the alkylene oxide chain, and bisphenol A modified with alkylene oxide. And compounds in which a (meth)acryloyl group is added to both ends of the alkylene oxide chain.

In the compound (B2), the alkylene oxide chain in the compound having (meth)acryloyl groups at both ends of the alkylene oxide chain contains at least two alkylene oxides selected from ethylene oxide and propylene oxide. It is a connected group. When the compound (B2) contains both ethylene oxide and propylene oxide, these may be randomly or block-connected, or a random linking site and a block linking site may be mixed.

As such a compound (B2), for example, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, hepta ethylene glycol di (meth) acrylic Rate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, having (meth)acryloyl groups at both ends of the 12 mol ethylene oxide chain Compound, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, and an average of 3 mol of ethylene oxide are added to both ends of polypropylene glycol to which an average of 12 mol of propylene oxide is added Dimethacrylate of one glycol, dimethacrylate of glycol in which an average of 15 moles of ethylene oxide is further added to both ends of polypropylene glycol to which an average of 18 moles of propylene oxide is added. More specifically, FA-023M, FA-024M, and FA-027M (manufactured by Hitachi Chemical Industries), and the like can be mentioned. These are preferable from the viewpoints of flexibility, resolution, and adhesion.

In the compound (B2), as a compound in which (meth)acryloyl groups are added to both ends of the alkylene oxide chain of alkylene oxide-modified bisphenol A, specifically, for example, the following general formula (I):

[Formula 4]

{In formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n1 and n3 are each independently, It is an integer of 1 to 39, and n1 + n3 is an integer of 2 to 40, n2 and n4 are each independently an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30, -(AO The arrangement of the repeating units of )- and -(BO)- may be random or block, and in the case of a block, either of the -(AO)-block and the -(BO)-block may be on the bisphenyl group side. It may be a compound represented by }.

As such a compound (B2), for example, Dimethacrylate of polyethylene glycol which added an average of 5 moles of ethylene oxide to both ends of bisphenol A, respectively; Dimethacrylate of polyethylene glycol to which an average of 2 moles of ethylene oxide was added to both ends of bisphenol A; And dimethacrylate of polyethylene glycol in which an average of 1 mol of ethylene oxide is added to both ends of bisphenol A, respectively, from the viewpoints of resolution and adhesion, and the like are preferable.

In the compound (B2), the compound having 3 or more (meth)acryloyl groups has, for example, 3 moles or more of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and ethyleneoxy group or propylene The compound obtained by making the alcohol obtained by adding an oxy group into (meth)acrylate is mentioned. In this case, examples of the compound that can serve as the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanurate ring, and the like. These tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, hexa(meth)acrylate, etc. can be used as a compound (B2) having 3 or more (meth)acryloyl groups. .

In the compound (B2), as the tri(meth)acrylate, for example, ethoxylated glycerin tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylic Rate, trimethylolpropane tri(meth)acrylate, etc. are mentioned. Among trimethylolpropane tri(meth)acrylate, for example, trimethacrylate in which an average of 21 moles of ethylene oxide is added to trimethylolpropane, trimethacrylate in which an average of 30 moles of ethylene oxide is added to trimethylolpropane, etc. Silver is preferable from the viewpoints of flexibility, adhesion, and bleed-out suppression.

In the compound (B2), as the tetra(meth)acrylate, for example, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate And the like. Among these, pentaerythritol tetra(meth)acrylate is preferable. The pentaerythritol tetra(meth)acrylate is preferably a tetra(meth)acrylate in which 1 mol or more and 40 mol or less of alkylene oxide is added to the four terminals of pentaerythritol.

In the compound (B2), as penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. are mentioned, for example.

In the compound (B2), as hexa(meth)acrylate, for example, hexa(meth)acrylate and dipentaerythritol in which 1 mol or more and 40 mol or less of ethylene oxide are added in total to the six ends of dipentaerythritol. Hexa(meth)acrylate etc. in which 1 mol or more and 20 mol or less of ε-caprolactone is added to the six terminals of pentaerythritol in total are preferable.

Compound (B2) may consist of only one type of compound or may be a mixture of two or more types of compounds.

When compound (B) contains compound (B1) and compound (B2), the amount of compound (B1) is based on the total mass of compound (B), preferably 5% by mass or more and 7% by mass It is 8 mass% or more, 9 mass% or more, or 10 mass% or more. The amount of compound (B1) is, based on the total mass of compound (B), preferably 50% by mass or less, 30% by mass or less, and 20% by mass or less.

In the case where the compound (B) contains the compound (B1), particularly preferred embodiments are described in the following [Aspect 1] to [Aspect 18].

[Mode 1]

As a photosensitive resin composition for obtaining a resist pattern by performing exposure, heating, and development in this order,

The photosensitive resin composition, based on the total solid content mass of the photosensitive resin composition, the following components:

(A) 10 mass% or more and 90 mass% or less alkali-soluble polymer;

(B) 5% by mass or more and 70% by mass or less of a compound having an ethylenically unsaturated double bond;

(C) 0.01 mass% or more and 20 mass% or less photoinitiator

Including, and,

The compound (B) having an ethylenically unsaturated double bond is represented by the following general formula (II):

[Formula 5]

{In formula (II), A is a C4 or more divalent hydrocarbon group.} Containing a compound (B1) having a structure represented by,

Photosensitive resin composition.

[Mode 2]

The photosensitive resin composition according to Aspect 1, wherein the compound (B1) is a compound having two or more ethylenically unsaturated double bonds.

[Mode 3]

The compound (B1) is the following general formula (III):

[Formula 6]

(In formula (III), A is a C4-8 divalent hydrocarbon group, B ¹ and B ² are each independently an ethylene group or a propylene group, (B ¹ -O), (AO), and The arrangement of (B ² -O) may be random or block, n1 is an integer from 0 to 50, n2 is an integer from 2 to 100, n3 is an integer from 0 to 50, and R ¹ and R ² are, Each independently represents a hydrogen atom or a methyl group. The photosensitive resin composition according to Aspect 1 or 2, which is a compound represented by }.

[Mode 4]

The photosensitive resin composition according to Aspect 3, wherein n1 and n3 in the general formula (III) are each independently an integer of 0 to 30.

[Mode 5]

In the general formula (III), the photosensitive resin composition according to Aspect 3 or 4, wherein n1 + n3 is an integer of 0 to 10.

[Mode 6]

The photosensitive resin composition according to any one of Aspects 1 to 5, wherein A in the general formula (III) is a C4 divalent hydrocarbon group.

[Mode 7]

In aspects 1 to 6, wherein the compound (B) having an ethylenically unsaturated double bond further comprises a compound (B2) having an ethylenically unsaturated double bond and not having a structure represented by the general formula (II) The photosensitive resin composition according to any one of claims.

[Mode 8]

The photosensitive resin composition in any one of Aspects 1-7 which further contains a photosensitizer.

[Mode 9]

The photosensitive resin composition according to Aspect 8, wherein the photosensitizer contains an anthracene compound.

[Mode 10]

The photosensitive resin composition according to Aspect 8 or 9, wherein the photosensitizer contains a pyrazoline compound.

[Mode 11]

The photosensitive resin composition according to any one of Aspects 1 to 10, wherein the photopolymerization initiator (C) contains an imidazole compound.

[Mode 12]

With the support layer,

The layer of the photosensitive resin composition in any one of Aspects 1-11 on the said support layer

Having a photosensitive resin laminate.

[Mode 13]

The following process:

Step of exposing the layer of the photosensitive resin composition according to any one of Aspects 1 to 11;

A heating step of heating the layer of the photosensitive resin composition after the exposure step; And

A developing step of developing the layer of the photosensitive resin composition after the heating step;

A method of forming a resist pattern comprising a.

[Mode 14]

The method for forming a resist pattern according to Aspect 13, wherein the heating temperature in the heating step is in the range of 30°C or more and 150°C or less.

[Mode 15]

The method for forming a resist pattern according to Aspect 13 or 14, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens.

[Mode 16]

The method for forming a resist pattern according to Aspect 13 or 14, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern.

[Mode 17]

The method for forming a resist pattern according to Embodiment 16, wherein the exposure step is performed by a method of exposing with a first laser light having a center wavelength of less than 390 nm and a second laser light having a center wavelength of 390 nm or more.

[Mode 18]

The method for forming a resist pattern according to Aspect 17, wherein the center wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less.

<(C) Photoinitiator>

The photoinitiator (C) is a compound that polymerizes a monomer by light, and may be a photoinitiator generally known in the art.

The amount of the photoinitiator in the photosensitive resin composition is based on the total solid content mass of the photosensitive resin composition, preferably 0.01 to 20% by mass, 0.05% by mass to 10% by mass, 0.1% by mass to 7% by mass, or 0.1 It is mass%-6 mass %. When the total amount of the photopolymerization initiator is 0.01% by mass or more, sufficient sensitivity can be obtained, and when 20% by mass or less, light is sufficiently transmitted to the bottom of the resist, and good high resolution can be obtained.

As photoinitiators, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin or benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime esters Compounds, acridine compounds, hexaarylbiimidazole, pyrazoline compounds, anthracene compounds, coumarin compounds, N-arylamino acids or ester compounds thereof, and halogen compounds.

As an aromatic ketone compound, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, 4-methoxy- 4'-dimethylaminobenzophenone is mentioned. Among these, 4,4'-bis(diethylamino)benzophenone is preferable from the viewpoint of adhesiveness. From the viewpoint of transmittance, the content of the aromatic ketone compound in the photosensitive resin composition is, based on the total solid content mass of the photosensitive resin composition, preferably 0.01% by mass to 0.5% by mass, or 0.02% by mass to 0.3% by mass.

As the acridine compound, for example, 9-phenylacridine, bisacridinylheptane, 9-(p-methylphenyl)acridine, and 9-(m-methylphenyl)acridine, It is preferable in terms of resolution and adhesion. The anthracene compound is preferably an anthracene derivative having an alkoxy group having 1 to 40 carbon atoms which may have a substituent and/or an aryl group having 6 to 40 carbon atoms which may have a substituent at position 9 and/or 10, for example , 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene are preferable in terms of sensitivity, resolution, and adhesion. As the coumarin compound, for example, 7-diethylamino-4-methylcoumarin is preferable in terms of sensitivity, resolution, and adhesion. As the N-arylamino acid or its ester compound, for example, N-phenylglycine is preferable in terms of sensitivity, resolution, and adhesion. As the halogen compound, tribromomethylphenylsulfone is preferable, for example. In addition, as photoinitiator, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -One, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and triphenylphosphine oxide are also mentioned.

As hexaarylbiimidazole, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris-(o-chlorophenyl)-4-(3,4- Dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2, 4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2, 2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3- Difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4 ,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5 '-Tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3 -Methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl) -Biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'- Bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2, 4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5 -Tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluoro Lophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluoro Rophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and the like. From the viewpoint of high sensitivity, resolution, and adhesion, the hexaarylbiimidazole is preferably a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. The amount of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass, 0.1% by mass to 6% by mass, or from the viewpoint of improving the peeling property and/or sensitivity of the photosensitive resin layer. It is in the range of 1 mass%-5 mass %.

A photoinitiator may be used alone or in combination of two or more.

<Photosensitizer>

The photosensitive resin composition may further contain a photosensitizer from the viewpoint of improving the high transmittance, the peeling property of the photosensitive resin layer, and/or the sensitivity. As a photosensitizer, a pyrazoline compound and an anthracene compound are mentioned. The content of the photosensitizer in the photosensitive resin composition is based on the total solid content mass of the photosensitive resin composition, preferably 0.01% by mass to 10% by mass, 0.05% by mass to 5% by mass, 0.1% by mass to 3% by mass It is 0.1 mass%-1 mass %, or 0.1 mass%-0.7 mass %. If the amount of the photosensitizer is 0.01% by mass or more, the peeling characteristics and sensitivity of the photosensitive resin layer can be further improved. When the amount of the photosensitizer is 10% by mass or less, the light transmittance of the photosensitive resin layer is maintained at a high level, which is preferable from the viewpoint of exposure efficiency.

As a pyrazoline compound, for example, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzooxa Zol-2-yl)phenyl)-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)- 5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, 1-phenyl-3-( 4-Isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1 -Phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5- (3,4-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3 -(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3 -Dimethoxyphenyl)-pyrazoline, and 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline. As the pyrazoline compound, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline is more preferable.

As an anthracene compound, a dialkoxyanthracene compound such as 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene, for example, has sensitivity, resolution, and adhesion. It is preferable in

<Phenol derivative>

From the viewpoint of resolution and adhesion, it is preferable that the photosensitive resin composition further contains a phenol derivative. As a phenol derivative, for example, p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4 -Methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5- Di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis(2-hydroxy-3-t -Butyl-5-ethylphenyl)methane, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3 -(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di -t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di- t-butyl-4-hydroxybenzylphosphonate-diethylester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene , Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'- Butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrenated phenol (e.g. Kawaguchi Chemical Industries Co., Ltd. make, Antage SP), tribenzylphenol (for example, Kawaguchi Chemical Industries Co., Ltd. make, TBP, a phenol having 1 to 3 benzyl groups), and biphenols are mentioned. .

The amount of the phenol derivative in the photosensitive resin composition is preferably 0.001% by mass to 10% by mass, based on the total solid content mass of the photosensitive resin composition. From the viewpoint of resolution and adhesion, the lower limit of the amount of the phenol derivative is more preferably 0.005% by mass or more, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more. From the viewpoint of less decrease in sensitivity and improvement in resolution, the lower limit of the amount of the phenol derivative is more preferably 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, or 0.3% by mass Below.

<Additive>

The photosensitive resin composition may contain additives, such as a coloring agent, a stabilizer, an adhesion aid, and a plasticizer, as desired. For example, additives listed in Japanese Unexamined Patent Application Publication No. 2013-156369 may be used.

(coloring agent)

In this embodiment, the photosensitive resin composition may further contain at least 1 type selected from the group consisting of a colorant, for example, a dye and a colored substance, as desired.

As a coloring substance, for example, fuchsin, phthalocyanine green, oramine base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (e.g., manufactured by Hodogaya Chemical Co., Ltd., Eisen (Registered trademark) MALACHITE GREEN), basic blue 20, and diamond green (for example, Hodogaya Chemical Co., Ltd. make, Aizen (registered trademark) DIAMOND GREEN GH) are mentioned. The amount of the colored substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass based on the total solid content mass of the photosensitive resin composition. When the amount of the colored substance is 0.001 mass% or more, the handling property of the photosensitive resin composition is improved. When the amount of the colored substance is 1% by mass or less, storage stability of the photosensitive resin composition is easily maintained.

The photosensitive resin composition is preferable from the viewpoint of visibility because the exposed portion is colored by containing a dye. When the inspection machine or the like reads the alignment markers for exposure, the higher the contrast between the exposed portion and the unexposed portion is easier to recognize and is advantageous. From this point of view, preferred dyes include leuco dyes and fluorane dyes. Examples of the leuco dye include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], and the like. From the viewpoint of improving the contrast, as a leuco dye, leuco crystal violet is more preferable. The amount of the dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass, based on the total solid content mass of the photosensitive resin composition. When the amount of the dye is 0.1% by mass or more, the contrast between the exposed portion and the unexposed portion becomes better. The amount of the dye is more preferably 0.2% by mass or more, or 0.4% by mass or more. When the amount of the dye is 10% by mass or less, the storage stability of the photosensitive resin composition is easily maintained. The amount of the dye is more preferably 5% by mass or less, or 2% by mass or less.

From the viewpoint of optimizing adhesion and contrast, the photosensitive resin composition preferably contains a combination of a leuco dye and a halogen compound described in the column of "(C) Photoinitiator". When a leuco dye is used in combination with a halogen compound, if the amount of the halogen compound in the photosensitive resin composition is 0.01% by mass to 3% by mass based on the total solid content of the photosensitive resin composition, the storage stability of the color in the photosensitive layer is maintained. Easy to become

(Stabilizer)

The photosensitive resin composition may further contain a stabilizer in order to improve thermal stability and storage stability. The stabilizer may be, for example, at least one compound selected from the group consisting of a radical polymerization inhibitor, a benzotriazole compound, and a carboxybenzotriazole compound.

Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosoamine. In order not to impair the sensitivity of the photosensitive resin composition, a nitrosophenylhydroxyamine aluminum salt is preferred.

As a benzotriazole compound, for example, 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2 ,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotria Sol, etc. are mentioned.

As the carboxybenzotriazole compound, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2 -Ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylenecarboxy Benzotriazole, etc. are mentioned.

The total amount of the stabilizer in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass, or 0.05% by mass to 1% by mass, based on the total solid content mass of the photosensitive resin composition. When the total amount of the stabilizer is 0.01% by mass or more, high storage stability can be imparted to the photosensitive resin composition. When the total amount of the stabilizer is 3% by mass or less, it is preferable from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye. Discoloration of the dye can be measured with a transmittance of a wavelength of 630 nm. The high transmittance at a wavelength of 630 nm indicates that the dye is discolored. The transmittance at a wavelength of 630 nm of the laminate of the support layer and the photosensitive resin composition layer is preferably 80% or less, 78% or less, 75% or less, 72% or less, 70% or less, 68% or less, 65% or less , 62% or less, 60% or less, 58% or less, 55% or less, 52% or less, or 50% or less. This transmittance is a transmittance as a laminate of the support layer and the photosensitive resin composition layer, and does not include a protective layer.

(Adhesive aid)

The photosensitive resin composition may further contain an epoxy compound of bisphenol A. Examples of the epoxy compound of bisphenol A include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidating the terminal.

(Plasticizer)

The photosensitive resin composition may further contain a plasticizer. As a plasticizer, for example, a phthalic acid ester compound (e.g., diethylphthalate), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri acetyl citrate -n-propyl, tri-n-butyl acetylcitrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. More specifically, adecanol SDX-1569, adecanol SDX-1570, adecanol SDX-1571, and adecanol SDX-479 (manufactured by Asahi Telephone Co., Ltd.); New Paul BP-23P, New Paul BP-3P, New Paul BP-5P, New Paul BPE-20T, New Paul BPE-60, New Paul BPE-100, and New Paul BPE-180 (manufactured by Sanyo Chemical Co., Ltd.); Uniall DB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA-400, and Uniol DA-700 (manufactured by Nippon Oil Co., Ltd.); And compounds having a bisphenol skeleton such as BA-P4U glycol and BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.) can be mentioned.

The amount of the plasticizer in the photosensitive resin composition is based on the total solid content mass of the photosensitive resin composition, preferably 1 to 50% by mass, or 1 to 30% by mass. When the amount of the plasticizer is 1% by mass or more, it is preferable from the viewpoint of suppressing the delay in development time and providing flexibility to the cured film. When the amount of the plasticizer is 50% by mass or less, it is preferable from the viewpoint of suppressing insufficient hardening and cold flow.

<solvent>

The photosensitive resin composition can be dissolved in a solvent and used in the manufacture of a photosensitive resin laminate in the form of a photosensitive resin composition combination liquid. As a solvent, a ketone compound, an alcohol compound, etc. are mentioned. As a ketone compound, methyl ethyl ketone (MEK) and acetone are mentioned. As an alcohol compound, methanol, ethanol, and isopropanol are mentioned. The amount of the solvent added to the photosensitive resin composition is preferably an amount such that the viscosity at 25°C of the photosensitive resin composition combination liquid applied on the support layer is 500 mPa·s to 4,000 mPa·s.

When the amount of water in the photosensitive resin composition is large, local plasticization of the photosensitive resin composition is rapidly accelerated, and an edge fuse may be generated, so from the viewpoint of suppressing the edge fuse, it is preferable that the amount of water in the photosensitive resin composition is small. The moisture content in the photosensitive resin composition is preferably 0.7% by mass or less based on the mass of the photosensitive resin composition after applying the combination solution of the photosensitive resin composition to the support layer and drying it (moisture content after drying). The moisture content after drying in the photosensitive resin composition is more preferably 0.65 mass% or less, 0.6 mass% or less, 0.55 mass% or less, 0.5 mass% or less, 0.45 mass% or less, 0.4 mass% or less, 0.35 mass% or less, 0.3 It is mass% or less, 0.25 mass% or less, or 0.2 mass% or less.

[Photosensitive resin laminate]

In this embodiment, the photosensitive resin laminated body of the present invention has a support layer and a layer of the photosensitive resin composition of the present embodiment (hereinafter, also referred to as "photosensitive resin layer") on the support layer. On the photosensitive resin layer, you may have a protective layer further.

<Support layer>

As the supporting layer, a transparent supporting film that transmits light emitted from an exposure light source is preferable. As a support film, for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film , Polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. As a support layer, you may use a support film stretched as needed.

From the viewpoint of suppressing light scattering during exposure, the support layer preferably has a haze of 5% or less, 2% or less, 1.5% or less, or 1.0% or less. From the same viewpoint, the surface roughness Ra of the surface of the support layer in contact with the photosensitive layer is preferably 30 nm or less, 20 nm or less, or 10 nm or less. The thinner the thickness of the support layer is, the more advantageous it is to improve the image formability and economic efficiency. However, in order to maintain the strength of the photosensitive resin laminate, it is preferably 10 µm to 30 µm. The supporting layer may contain fine particles such as a lubricant as desired. It is preferable that the size of the fine particles is less than 5 μm.

The support layer may have a single-layer structure or a multilayer structure in which resin layers formed of a plurality of compositions are laminated. In the case of a multilayer structure, an antistatic layer may be provided. Examples of the multilayer structure include a two-layer support layer having a resin layer on one side of the substrate, and a three-layer support layer having resin layers on both surfaces of the substrate, for example. As an aspect of the three-layered support layer, for example, as a substrate, using the support film illustrated above, having a resin layer containing fine particles on one side A, and on the other side B,

(1) It has a resin layer containing approximately the same amount of fine particles as the resin layer on the side A side;

(2) It has a resin layer containing a small amount of fine particles than the resin layer on the side A side;

(3) It has a resin layer containing fine particles finer than the fine particles contained in the resin layer on the side A side; And

(4) It has a resin layer that does not contain fine particles

Aspects, such as, are mentioned. In the case of the structures of the above (2), (3) and (4), it is preferable to have a photosensitive resin layer on the side B side. In this case, if there is a resin layer containing fine particles on the surface A side opposite to the photosensitive resin layer, it is preferable from the viewpoint of the sliding property of the film. It is preferable that the size of the fine particles contained in the resin layer is less than 1.5 µm.

<Photosensitive resin layer>

The photosensitive resin layered product has a photosensitive resin layer on a support layer. The photosensitive resin layer is a layer formed from the photosensitive resin composition of the present embodiment. The thickness of the photosensitive resin layer in the photosensitive resin layered product is different depending on the application, but is preferably 1 µm to 300 µm, 3 µm to 100 µm, 5 µm to 60 µm, or 10 µm to 30 µm. When the thickness of the photosensitive resin layer is 1 μm or more, the film strength becomes higher. When the thickness of the photosensitive resin layer is 300 µm or less, the resolution becomes higher.

<Protective layer>

The photosensitive resin layered product may have a photosensitive resin layer on the support layer, and may further have a protective layer on this photosensitive resin layer. An important characteristic of the protective layer used in the photosensitive resin layered product is that the adhesive force with the photosensitive resin layer is sufficiently smaller than that of the support layer and can be easily peeled off. As the protective layer, for example, a protective film such as a polyethylene film or a polypropylene film can be used. It is also possible to use a film described in Japanese Patent Application Laid-Open No. 59-202457 and having excellent peelability. The thickness of the protective layer is preferably 10 µm to 100 µm, more preferably 10 µm to 50 µm.

A gel called fish may be present on the surface of the polyethylene film. When a polyethylene film having fisheye is used as a protective film, the fisheye may be transferred to the photosensitive resin layer. When the fisheye is transferred to the photosensitive resin layer, air may be drawn in at the time of lamination to form voids, leading to defects in the resist pattern. From the viewpoint of preventing fisheye, the material of the protective layer is preferably oriented polypropylene. As a specific example, Oji Paper Co., Ltd. product, Alpan E-200A is mentioned.

[Method of manufacturing photosensitive resin laminate]

An example of a method of manufacturing a photosensitive resin laminate using the photosensitive resin composition of the present embodiment will be described. The photosensitive resin laminate can be manufactured by sequentially laminating a support layer, a photosensitive resin layer, and a protective layer as necessary. For example, first, the photosensitive resin composition of this embodiment is mixed with a solvent which dissolves it, and the combination liquid of a uniform photosensitive resin composition is prepared. A photosensitive resin layer made of a photosensitive resin composition can be laminated on the support layer by applying the combination solution of the photosensitive resin composition to the support layer using a bar coater or a roll coater, and then drying to remove the solvent. Then, if necessary, a photosensitive resin laminate can be manufactured by laminating a protective layer on the photosensitive resin layer.

[Method of manufacturing resist pattern]

An example of a method of manufacturing a resist pattern using the photosensitive resin laminate of the present embodiment will be described. The method for producing a resist pattern of the present embodiment is the following steps:

Step of exposing the layer (photosensitive resin layer) of the photosensitive resin composition of the present embodiment;

A heating step of heating the exposed photosensitive resin layer; And

And a developing step of developing the heated photosensitive resin layer.

The photosensitive resin layer exposed in the exposure step is typically laminated on a substrate. The method for forming a resist pattern of the present embodiment may include a lamination step of laminating a photosensitive resin layer on a substrate prior to the exposure step.

As a resist pattern, for example, a printed wiring board, a semiconductor element, a printing board, a liquid crystal display panel, a touch panel, a flexible substrate, a lead frame substrate, a COF (chip-on film) substrate, a semiconductor package substrate, a liquid crystal transparent electrode, Patterns, such as a wiring for liquid crystal TFT, and an electrode for PDP (plasma display panel), are mentioned.

<Lamination process>

In the laminating process, a photosensitive resin layer is formed on the substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled, and then the photosensitive resin layer is heated and press-bonded to the substrate surface with a laminator to laminate. Examples of the material of the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO).

The photosensitive resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides as necessary. The heating temperature at the time of lamination is generally 40°C to 160°C. By performing heat compression bonding at the time of lamination two or more times, the adhesion of the obtained resist pattern to the substrate may be improved. At the time of heat-compression bonding, a two-stage laminator provided with two rolls may be used, or a laminate of a substrate and a photosensitive resin layer may be repeatedly passed through a roll several times for compression bonding.

<Exposure process>

In the exposure process, the photosensitive resin layer is exposed. As an exposure method, an exposure method in which a mask film having a desired wiring pattern is brought into close contact with the support layer and is performed using an active light source; An exposure method by direct drawing of a drawing pattern which is a desired wiring pattern; And an exposure method by projecting an image of a photomask through a lens.

As the exposure method, an exposure method by direct drawing of a drawing pattern, or an exposure method in which an image of a photomask is projected through a lens is preferable, and an exposure method by direct drawing of a drawing pattern is more preferable. The advantage of the photosensitive resin composition according to the present embodiment is more remarkable in an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens, and exposure by direct drawing of a drawing pattern It is particularly remarkable in the method.

When the exposure step is an exposure method by direct drawing, it is preferable that it is a laser light having a center wavelength of less than 390 nm or a laser light having a center wavelength of 390 nm or more. It is more preferable that it is a laser light having a center wavelength of 350 nm or more and 380 nm or less, or a laser light having a center wavelength of 400 nm or more and 410 nm or less. It is preferable to perform exposure by a method of exposing with a first laser light having a center wavelength of less than 390 nm and a second laser light having a center wavelength of 390 nm or more. Moreover, it is more preferable that the center wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less.

<Heating process>

In the heating step, the exposed photosensitive resin is heated (heating after exposure). The heating temperature is preferably 30°C to 150°C, more preferably 60°C to 120°C. By performing this heating process, resolution and adhesion are improved. As the heating method, hot air, infrared rays, far infrared rays, thermostats, hot plates, hot air dryers, infrared dryers, hot rolls, and the like can be used. If the heating method is a hot roll, since it can be processed in a short time, it is preferable, and two or more hot rolls are more preferable.

The elapsed time from exposure to heating, more precisely, the elapsed time from the time when exposure is stopped to the time when the temperature rise is started is preferably within 15 minutes or within 10 minutes. The elapsed time from the time when exposure is stopped to the time temperature rise is started is 10 seconds or more, 20 seconds or more, 30 seconds or more, 1 minute or more, 2 minutes or more, 3 minutes or more, 4 minutes or more, or 5 minutes or more. do.

<Development process>

In the developing step, the photosensitive resin layer is developed. For example, after exposure, the support layer on the photosensitive resin layer is peeled off, and then a resist pattern can be formed on the substrate by developing and removing the unexposed portion using a developer of an aqueous alkali solution.

As the aqueous alkali solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is used. The alkaline aqueous solution is appropriately selected in accordance with the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% by mass to about 2% by mass and about 20°C to about 40°C is preferable.

[Method of manufacturing circuit board]

A circuit board can be manufactured using a substrate having a resist pattern formed by the above method. The circuit board manufacturing method of the present embodiment includes a circuit formation step of forming a circuit board by etching or plating the substrate having the resist pattern of the present embodiment.

<Circuit formation process>

In the circuit formation step, a circuit is formed by etching or plating a substrate having a resist pattern. Specifically, the surface of the substrate exposed by the development (for example, the copper surface of the copper clad laminate) is etched or plated to produce a conductor pattern.

<Peeling process>

The circuit board manufacturing method of the present embodiment may further include a peeling step of typically removing the resist pattern from the substrate after the circuit forming step. The resist pattern is peeled from the substrate using an appropriate stripper. Examples of the peeling solution include an aqueous alkali solution and an amine type peeling solution. However, the resist pattern formed by heating after exposure from the photosensitive resin composition of the present invention exhibits good peelability with respect to an amine-based peeling solution, and excessive miniaturization of peeling pieces is suppressed. Therefore, when an amine-based stripping solution is used as the stripping solution, the advantageous effects of the present invention are exhibited more favorably.

The amine contained in the amine stripper may be an inorganic amine or an organic amine. As an inorganic amine, ammonia, hydroxylamine, hydrazine, etc. are mentioned, for example. Examples of the organic amine include ethanolamine, propanolamine, alkylamine, cyclic amine, and quaternary ammonium salt.

As ethanolamine, for example, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, amino Ethoxyethanol, etc. are mentioned. As propanolamine, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, etc. are mentioned, for example. Examples of the alkylamine include monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, and tetraethylenepentamine. As a cyclic amine, choline, morpholine, etc. are mentioned, for example. Examples of the quaternary ammonium salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl)ammonium hydroxide, N ,N-diethyl-N,N-di(2-hydroxyethyl)ammonium hydroxide, and the like.

The amine-based release agent used in the present invention may be an aqueous solution containing one or more of the amines illustrated above. The concentration of the amine in the aqueous solution may be appropriately set depending on the purpose, the composition of the photosensitive resin layer, development conditions, and the like.

The amine-based release agent used in the present invention may further contain additives commonly used in the release agent, for example, a surfactant, a defoaming agent, a pH adjuster, a preservative, an anti-reposition agent, and the like.

The peeling process is, for example, at a temperature of 0°C or more and 100°C or less, preferably room temperature (23°C) or more and 50°C or less, for example, 1 second or more and 1 hour or less, and preferably 10 seconds or more and 10 minutes. In the following time, it is carried out.

After the peeling step, as desired, the substrate after removing the resist pattern may be washed with pure water or the like.

The photosensitive resin laminate of this embodiment is a conductor such as a printed wiring board, a flexible substrate, a lead frame substrate, a touch panel substrate, a COF substrate, a semiconductor package substrate, a liquid crystal transparent electrode, a liquid crystal TFT wiring, and a PDP electrode. It is a photosensitive resin laminate suitable for manufacture of a pattern.

Example

Hereinafter, embodiments of the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

[Examples 1 to 8 and Comparative Examples 1 to 4]

<Production of photosensitive resin laminate>

As shown in Tables 1-3 mentioned later, each component (however, the amount of each component represents the compounding quantity (mass part) as a solid content) was sufficiently stirred and mixed, and the photosensitive resin composition combination liquid was obtained. In Tables 2 and 3, the I value of the binder represents the I value as a mixture of alkali-soluble polymers represented by symbols A-1 to A-3. A 16 µm-thick polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB-40) was used as a supporting film, and this combination solution was uniformly applied to the surface of the film using a bar coater, and 3 in a dryer at 95°C. It dried for a minute to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 25 µm. Next, on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film is not laminated, as a protective layer, a 19 μm-thick polyethylene film (manufactured by Tama Poly Co., Ltd., GF-818) was bonded to each other. A photosensitive resin laminate was obtained.

<The front of the substrate (整面)>

As a substrate for evaluation of image quality, a 0.4 mm thick copper clad laminate laminated with 35 μm rolled copper foil was subjected to jet scrub polishing using a spray pressure of 0.2 MPa (manufactured by Ujiden Chemical Co., Ltd., #400). And a 10% by mass H ₂ SO ₄ aqueous solution to wash the substrate surface.

<Laminate>

While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, to a copper clad laminate preheated to 50°C, a hot roll laminator (manufactured by Asahi Chemical Co., Ltd., AL-700) was used to roll the photosensitive resin laminate at a roll temperature. It laminated at 105 degreeC. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m/min.

<Exposure>

A stopper 41-step step tablet was used on the substrate for evaluation 2 hours after lamination by a direct drawing exposure machine (manufactured by Orvotech Co., Ltd., Nuvogo1000, light source: 375 nm (30%) + 405 nm (70%)) And exposed. The exposure was performed at an exposure amount of 18 stages of the highest remaining film stage when exposed and developed using the stopper 41 stage step tablet as a mask.

<Heating after exposure>

The substrate for evaluation, which had passed 1 minute after exposure, was heated by a hot roll laminator (manufactured by Asahi Chemical Co., Ltd., AL-700). The roll temperature was 105°C, the air pressure was 0.30 MPa, and the lamination speed was 1.5 m/min. Moreover, the evaluation board|substrate prepared separately was used, and after 7 minutes passed after exposure, it heated similarly. In addition, since the effect of heating is reduced when the elapsed time after exposure is increased, heating is usually performed in about 1 minute after exposure. Therefore, heating 7 minutes after exposure in this example is a very strict condition.

<phenomena>

After peeling the polyethylene terephthalate film (support layer), using an alkali developing device (manufactured by Fuji pores, developing device for dry films), a 30° C. 1% by mass Na ₂ CO ₃ aqueous solution was sprayed over a predetermined period of time to develop. . The time of the developing spray was made twice as long as the shortest developing time, and the time of the water washing spray after development was made three times the shortest developing time. At this time, the shortest time required to completely dissolve the photosensitive resin layer in the unexposed portion was taken as the shortest development time.

<burning evaluation>

The minimum line width in which the pattern of mask pattern L/S = X µm/200 µm is normally formed was measured with an optical microscope. This measurement was performed for eight lines, and the average value of the eight line widths was determined as an index of adhesion. The adhesion was evaluated based on the following criteria.

A: The minimum adhesion line width of the independent pattern is less than 9 μm

B: The minimum adhesion line width of the independent pattern is 9 µm or more and less than 10 µm

C: The minimum adhesion line width of the independent pattern is 10 µm or more and less than 11 µm

D: Minimum adhesion line width of independent pattern is 11 ㎛ or more

The materials used in Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Table 1 below, and the results are shown in Tables 2 and 3 below.

[Examples 9 to 16 and Comparative Examples 5 to 8]

<Production of photosensitive resin laminate>

As shown in Tables 4 to 6 described later, each component (however, the amount of each component represents the amount (part by mass) as a solid content) was sufficiently stirred and mixed to obtain a photosensitive resin composition mixture. In Tables 5 and 6, the sp value (MPa ^1/2 ) of the binder represents the sp value as a mixture of alkali-soluble polymers represented by symbols A-1 to A-3. A 16 µm-thick polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB-40) was used as a supporting film, and this combination solution was uniformly applied to the surface of the film using a bar coater, and 3 in a 95°C dryer. It dried for a minute to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 25 µm. Subsequently, on the surface of the side where the polyethylene terephthalate film of the photosensitive resin composition layer is not laminated, as a protective layer, a 19 μm-thick polyethylene film (manufactured by Tama Poly Co., Ltd., GF-818) was bonded to the photosensitive resin laminate. Got it.

<Front of substrate>

As a substrate for evaluation of image quality, a 0.4 mm thick copper clad laminate laminated with 35 μm rolled copper foil was subjected to jet scrub polishing using a spray pressure of 0.2 MPa (manufactured by Ujiden Chemical Co., Ltd., #400). And a 10% by mass H ₂ SO ₄ aqueous solution to wash the substrate surface.

<Laminate>

While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, to a copper clad laminate preheated to 50°C, a hot roll laminator (manufactured by Asahi Chemical Co., Ltd., AL-700) was used to roll the photosensitive resin laminate at a roll temperature. It laminated at 105 degreeC. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m/min.

<Exposure>

A stopper 41-step step tablet was used on the substrate for evaluation 2 hours after lamination by a direct drawing exposure machine (manufactured by Orvotech Co., Ltd., Nuvogo1000, light source: 375 nm (30%) + 405 nm (70%)) And exposed. The exposure was performed at an exposure amount of 18 stages of the highest remaining film stage when exposed and developed using the stopper 41 stage step tablet as a mask.

<Heating after exposure>

The substrate for evaluation, which had passed 1 minute after exposure, was heated by a hot roll laminator (manufactured by Asahi Chemical Co., Ltd., AL-700). The roll temperature was 105°C, the air pressure was 0.30 MPa, and the lamination speed was 1.5 m/min. Moreover, the evaluation board|substrate prepared separately was used, and after 7 minutes passed after exposure, it heated similarly. In addition, since the effect of heating is reduced when the elapsed time after exposure is increased, heating is usually performed in about 1 minute after exposure. Therefore, heating after 7 minutes of exposure in this example is a very strict condition.

<phenomena>

After peeling the polyethylene terephthalate film (support layer), using an alkali developing device (manufactured by Fuji pores, developing device for dry films), a 30° C. 1% by mass Na ₂ CO ₃ aqueous solution was sprayed over a predetermined period of time to develop. . The time of the developing spray was made twice as long as the shortest developing time, and the time of the water washing spray after development was made three times the shortest developing time. At this time, the shortest time required to completely dissolve the photosensitive resin layer in the unexposed portion was taken as the shortest development time.

<burning evaluation>

The minimum line width in which the pattern of mask pattern L/S = X µm/200 µm is normally formed was measured with an optical microscope. This measurement was performed for eight lines, and the average value of the eight line widths was determined as an index of adhesion. The adhesion was evaluated based on the following criteria.

A: The minimum adhesion line width of the independent pattern is less than 9 μm

B: The minimum adhesion line width of the independent pattern is 9 µm or more and less than 10 µm

C: The minimum adhesion line width of the independent pattern is 10 µm or more and less than 11 µm

D: Minimum adhesion line width of independent pattern is 11 ㎛ or more

Materials used in Examples 9 to 16 and Comparative Examples 5 to 8 are shown in Table 4 below, and the results are shown in Tables 5 and 6 below.

[Examples 17 to 24 and Comparative Example 9]

<Measurement of the weight average molecular weight or number average molecular weight of the polymer>

The weight average molecular weight (Mw) or number average molecular weight (Mn) of the polymer is, Nippon Spectroscopy Co., Ltd., gel permeation chromatography (GPC) (pump: Gulliver, PU-1580 type, column: Showa Electric Co., Ltd.) Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Electric Works Co., Ltd.) It was calculated|required as polystyrene conversion by using the calibration curve by )). Further, the dispersion degree of the polymer was calculated as a ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn).

<Production of photosensitive resin laminate>

As shown in Tables 7 and 8 described later, each component (however, the amount of each component represents the compounding amount (parts by mass) as a solid content. "A-1 content" is the photosensitive resin composition of component A-1 shown in Table 7 The content (mass%) with respect to the solid content in is shown.) and the solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition combination liquid. A 16 µm-thick polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB-40) was used as a supporting film, and this combination solution was uniformly applied to the surface of the film using a bar coater, and 3 in a dryer at 95°C. It dried for a minute to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 25 µm. Subsequently, on the surface of the side where the polyethylene terephthalate film of the photosensitive resin composition layer is not laminated, as a protective layer, a 19 μm-thick polyethylene film (manufactured by Tama Poly Co., Ltd., GF-818) was bonded to the photosensitive resin laminate. Got it.

<Front of substrate>

As a substrate for evaluation of image quality, a 0.4 mm thick copper clad laminate laminated with 35 μm rolled copper foil was subjected to jet scrub polishing using a spray pressure of 0.2 MPa (manufactured by Ujiden Chemical Co., Ltd., #400). And a 10% by mass H ₂ SO ₄ aqueous solution to wash the substrate surface.

<Laminate>

Roll the photosensitive resin laminated body by a hot roll laminator (Asahi Chemical Co., Ltd. make, AL-700) to the copper clad laminated board preheated to 50 degreeC while peeling off the polyethylene film (protective layer) of the photosensitive resin laminated body Laminated at a temperature of 105°C. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m/min.

<Exposure>

A stopper 41-step step tablet was used on the substrate for evaluation 2 hours after lamination by a direct drawing exposure machine (manufactured by Orvotech Co., Ltd., Nuvogo1000, light source: 375 nm (30%) + 405 nm (70%)) And exposed. The exposure was performed at an exposure amount of 18 stages of the highest remaining film stage when exposed and developed using the stopper 41 stage step tablet as a mask.

<Heating after exposure>

The evaluation substrate 7 minutes after exposure was heated by a hot roll laminator (Asahi Chemical Co., Ltd. make, AL-700). The roll temperature was 105°C, the air pressure was 0.30 MPa, and the lamination speed was 1 m/min. Further, if the elapsed time after exposure is lengthened, the effect of heating is lost, and therefore, it is heated in about 1 minute after exposure. Therefore, heating 7 minutes after exposure in this example is a very strict condition.

<phenomena>

After peeling the polyethylene terephthalate film (support layer), using an alkali developing device (manufactured by Fuji pores, developing device for dry films), a 30° C. 1% by mass Na ₂ CO ₃ aqueous solution was sprayed over a predetermined period of time to develop. . The time of the developing spray was made twice as long as the shortest developing time, and the time of the water washing spray after development was made three times the shortest developing time. At this time, the shortest time required to completely dissolve the photosensitive resin layer in the unexposed portion was taken as the shortest development time.

<burning evaluation>

The minimum line width in which the pattern of mask pattern L/S = X µm/200 µm is normally formed was measured with an optical microscope. This measurement was performed for eight lines, and the average value of the eight line widths was determined as a value of adhesion.

Materials used in Examples 17 to 23 and Comparative Example 9 are shown in Table 7 below, and Table 8 below.

From the results of Tables 7 and 8, it was confirmed that the image quality evaluation results were superior to the comparative examples outside the scope of the present invention in the examples falling within the range of the constitutional requirements of the present invention.

The heating condition after exposure in this example is a very strict condition because it is heating 7 minutes after exposure. For example, when the compositions of Example 17 and Comparative Example 9 were developed without heating after exposure, the adhesion was all 10.6 µm. In short, in the composition of Comparative Example 9, no effect was observed in heating after 7 minutes of exposure, but in Example 23, even under very strict conditions, adhesion was improved. Moreover, in the conditions of heating 1 minute after exposure, the adhesiveness of 9.0 micrometer was obtained also in any of the compositions of Example 23 and Comparative Example 9.

From the above results, even when the adhesiveness is good in general heating conditions after exposure, the adhesiveness does not become good under strict conditions such as heating 7 minutes after exposure in this example. However, with the photosensitive resin composition of the present invention having a specific composition, it was possible for the first time to have good adhesion even under such difficult post-exposure heating conditions. Thereby, when manufacturing a circuit board, even if the elapsed time after exposure becomes long, good adhesion can be obtained, and a high-definition circuit pattern can be stably formed.

[Examples 24 to 38 and Comparative Examples 10 to 11]

<Measurement of the weight average molecular weight of the polymer>

The weight average molecular weight (Mw) of a polymer was calculated|required as a polystyrene conversion value by gel permeation chromatography (GPC) under the following conditions.

Measurement device: Nippon Spectroscopy Co., Ltd., gel permeation chromatography (GPC)

Pump: manufactured by Nippon Spectroscopy Co., Ltd., Gulliver PU-1580 type

Column: Showa Electric Co., Ltd. product, Shodex (registered trademark) KF-807, KF-806M, KF-806M, and KF-802.5 in series of 4

Mobile phase solvent: tetrahydrofuran

Standard sample: Showa Electric Works Co., Ltd., Shodex STANDARD SM-105

<Production of photosensitive resin laminate>

The photosensitive resin composition combination solution prepared in each Example and Comparative Example was uniformly applied on the surface of a polyethylene terephthalate film (manufactured by Toray Co., Ltd., FB-40, 16 μm thick) as a support layer using a bar coater, It dried for 3 minutes in a 95 degreeC dryer, and formed the photosensitive resin layer. The dry thickness of the photosensitive resin layer was 25 µm. Next, on the surface of the photosensitive resin layer on the side where the polyethylene terephthalate film is not laminated, a polyethylene film (manufactured by Tama Poly Co., Ltd., GF-818, 19 µm thickness) as a protective layer was bonded to each other, and a photosensitive resin laminated body Got it.

<Front of substrate>

As the substrate, a copper clad laminate having a thickness of 0.4 mm in which a rolled copper foil having a thickness of 35 μm was laminated was used. This copper-clad laminate was subjected to jet scrub polishing at a spray pressure of 0.2 MPa using a soft polishing (manufactured by Ujiden Chemical Co., Ltd., #400), and then surface washed with a 10% by mass H ₂ SO ₄ aqueous solution. , The substrate surface was faced.

<Laminate>

Using a hot roll laminator (manufactured by Asahi Chemical Co., Ltd., AL-700), a photosensitive resin laminate was laminated while peeling off a polyethylene film (protective layer) on a copper-clad laminate preheated to 50°C, and evaluated. A dragon substrate was obtained. At this time, the roll temperature was 105°C, the air pressure was 0.35 MPa, and the lamination speed was 1.5 m/min.

<Exposure>

On the substrate for evaluation after 2 hours elapsed after lamination, by a direct drawing exposure machine (manufactured by Orvotech Co., Ltd., Nuvogo Fine 10, light source: 375 nm (30%) + 405 nm (70%)), a stopper 41 step step tablet It was exposed using. The exposure was performed with the exposure using the stopper 41-step tablet as a mask, and the exposure amount at which the highest number of remaining film stages at the time of development was 19 stages.

<Heating after exposure>

The substrate for evaluation after 1 minute elapsed after exposure was heated with a hot roll laminator (manufactured by Asahi Chemical Co., Ltd., AL-700), and the photosensitive resin layer of the exposed portion was used as a cured film. The roll temperature was 105°C, the air pressure was 0.30 MPa, and the lamination speed was 1.5 m/min.

<phenomena>

After peeling the polyethylene terephthalate film (support layer) from the substrate for evaluation after exposure and heating, using an alkali developing device (manufactured by Fuji Pores, a developer for dry films), a 30° C. 1% by mass Na ₂ CO ₃ aqueous solution and pure water were prepared. , By spraying sequentially at each predetermined time, and developing. The time of the developing spray was made twice as long as the shortest developing time, and the time of the water washing spray after development was made three times the shortest developing time. Here, the shortest development time means the shortest time required for the photosensitive resin layer in the unexposed portion to be completely dissolved.

<Adhesion evaluation>

In the line-and-space test pattern in which the line width was varied at a constant value of 200 µm, the minimum line width normally formed was measured with an optical microscope. This measurement was performed for eight sets of test patterns, and the average value was used as an index of adhesion.

<Evaluation of peel time>

The substrate for evaluation, which had passed 2 hours after lamination, was exposed with a 5 cm long and 3 cm wide front pattern. The evaluation substrate 1 minute after exposure was heated by a hot roll laminator (Asahi Chemical Co., Ltd. make, AL-700). Subsequently, it developed at twice the minimum development time, and the time of the water washing spray after development was three times the shortest development time, and the evaluation sample was obtained. As a stripper, a mixed aqueous solution of R-100S (12 vol%) and R-101 (4 vol%) manufactured by Ryoko Chemical Co., Ltd. was heated at 50°C and used. The evaluation sample was immersed in a peeling solution, and the time until the cured film peeled from the substrate was recorded, and this time was taken as the peeling time and evaluated according to the following criteria.

A (good): peeling time is 45 seconds or less

B (possible): Peeling time exceeding 45 seconds and not exceeding 50 seconds

C (defect): peeling time exceeds 50 seconds

<Evaluation of peeling piece size>

In the evaluation of the peeling time, the evaluation sample was immersed in a peeling solution, the size of the cured film peeled off from the substrate was observed, and evaluated according to the following criteria.

AA (very good): The size of the peeling piece is 1 cm or more in width and height

A (Good): The size of the peeling piece is 7 mm or more and less than 1 cm

B (possible): The size of the peeling piece is 3 mm or more and less than 7 mm

C (defective): The size of the peeling piece is less than 3 mm in width and height

(A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator, and as an optional additive (D) a photosensitizer, a colorant, and a stabilizer, respectively, in Table 1 By mixing and sufficiently stirring ethanol as a component of the described kind and amount (parts by mass in terms of solid content) and a solvent, a photosensitive resin composition combination solution having a solid content concentration of 55% by mass was prepared.

The materials used in Examples 24 to 38 and Comparative Examples 10 to 11 are shown in Table 9 below, and the results are shown in Tables 10 to 12 below.

From the results of Tables 10 to 12, in the examples using the photosensitive resin composition of the present invention, at least one of adhesion properties, peeling time by an amine-based peeling solution, and peeling piece size, than the comparative examples outside the scope of the present invention, is preferable. It was confirmed that both were excellent.

Claims (29)

As a photosensitive resin composition for obtaining a cured resin product after exposure, heating and then developing, wherein the photosensitive resin composition includes the following components based on the total solid content mass of the photosensitive resin composition:
(A) 10% by mass to 90% by mass of alkali-soluble polymer,
(B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond, and
(C) 0.01% by mass to 20% by mass of a photopolymerization initiator,
The photosensitive resin composition, wherein the inorganic value (I value) of the alkali-soluble polymer (A) is 720 or less. The method of claim 1,
The photosensitive resin composition whose I value of the said alkali-soluble polymer (A) is 635 or less. The method of claim 2,
The photosensitive resin composition in which the I value of the said alkali-soluble polymer (A) is 600 or less. The method according to any one of claims 1 to 3,
The photosensitive resin composition, wherein the alkali-soluble polymer (A) has an I value of 300 or more. The method of claim 4,
The photosensitive resin composition, wherein the alkali-soluble polymer (A) has an I value of 400 or more. The method of claim 5,
The photosensitive resin composition, wherein the alkali-soluble polymer (A) has an I value of 450 or more. The method of claim 6,
The photosensitive resin composition in which the I value of the said alkali-soluble polymer (A) is 500 or more. The method of claim 7,
The photosensitive resin composition, wherein the alkali-soluble polymer (A) has an I value of 550 or more. As a photosensitive resin composition for obtaining a cured resin product after exposure, heating and then developing, wherein the photosensitive resin composition includes the following components based on the total solid content mass of the photosensitive resin composition:
(A) 10% by mass to 90% by mass of alkali-soluble polymer,
(B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond, and
(C) 0.01% by mass to 20% by mass of a photopolymerization initiator,
The photosensitive resin composition, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.45 MPa ^1/2 or less. The method of claim 9,
The photosensitive resin composition, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.40 MPa ^1/2 or less. The method of claim 10,
The photosensitive resin composition, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 21.20 MPa ^1/2 or less. The method according to any one of claims 9 to 11,
The photosensitive resin composition, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 19.00 MPa ^1/2 or more. The method of claim 12,
The photosensitive resin composition, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 19.50 MPa ^1/2 or more. The method of claim 13,
The photosensitive resin composition, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 20.00 MPa ^1/2 or more. The method of claim 14,
The photosensitive resin composition, wherein the solubility parameter (sp value) of the alkali-soluble polymer (A) is 20.50 MPa ^1/2 or more. As a photosensitive resin composition for obtaining a cured resin product after exposure, heating and then developing, wherein the photosensitive resin composition includes the following components based on the total solid content mass of the photosensitive resin composition:
(A) 10% by mass to 90% by mass of alkali-soluble polymer,
(B) 5% by mass to 70% by mass of a compound having an ethylenically unsaturated double bond, and
(C) 0.01% by mass to 20% by mass of a photopolymerization initiator,
The photosensitive resin composition includes, as the alkali-soluble polymer (A), an alkali-soluble polymer (A-1) containing 52% by mass or more of structural units derived from styrene and/or a styrene derivative as a monomer component, and the photosensitive resin composition The photosensitive resin composition containing 3 mass% or more based on the total solid content mass in in. The method of claim 16,
The photosensitive resin composition contains the alkali-soluble polymer (A-1) in an amount of 10 mass% or more with respect to the total solid content mass in the photosensitive resin composition. The method of claim 16 or 17,
The said alkali-soluble polymer (A-1) contains 55 mass% or more of structural units derived from styrene and/or a styrene derivative as a monomer component. The method of claim 18,
The said alkali-soluble polymer (A-1) contains 58 mass% or more of structural units derived from styrene and/or a styrene derivative as a monomer component. The method according to any one of claims 16 to 19,
The photosensitive resin composition, wherein the alkali-soluble polymer (A-1) contains 27% by mass or more of a structural unit derived from (meth)acrylic acid as a monomer component. The method according to any one of claims 16 to 19,
The photosensitive resin composition, wherein the alkali-soluble polymer (A-1) further contains a structural unit derived from benzyl (meth)acrylate as a monomer component. The following process:
A step of exposing the layer of the photosensitive resin composition according to any one of claims 1 to 21;
A heating step of heating the exposed layer of the photosensitive resin composition; And
A method of forming a resist pattern, comprising a developing step of developing the heated layer of the photosensitive resin composition. The method of claim 22,
The method for forming a resist pattern, wherein the heating temperature in the heating step is in the range of 30°C to 150°C. The method of claim 22 or 23,
The method for forming a resist pattern, wherein the heating step is performed within 15 minutes from stopping exposure. The method according to any one of claims 22 to 24,
A method of forming a resist pattern, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens. The method of claim 25,
A method of forming a resist pattern, wherein the exposure step is performed by an exposure method by direct drawing of a drawing pattern. The method of claim 26,
A method of forming a resist pattern, wherein the exposure step is performed by a method of exposing with a first laser light having a center wavelength of less than 390 nm and a second laser light having a center wavelength of 390 nm or more. The method of claim 27,
The method of forming a resist pattern, wherein the center wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less. A circuit board comprising forming a circuit board by manufacturing a resist pattern on a substrate by the method according to any one of claims 22 to 28, and performing etching or plating on the substrate having the resist pattern. Manufacturing method.